Certain para-cyclohexylcyclohexanol ethers of certain glycols



NOV. 13, v M DE GROOTE ET AL CERTAIN PARACYCLOHEXYLCYCLOHEXANOL ETHERS OF CERTAIN GLYCOLS Filed Nov 1, 1949 PARA CYCLOHEXYL- Ca -140 CYC LOHEXANOL 100o INVENTORS I MELV/N DE 6R00r ARTHUR F WIRTEL ATTORNEY Patented Nov. 13, 1951 T former.

CERTAIN PARA-CYCLOHEXYLCYCLOHEX- ANOL ETHERS OF CERTAIN GLYCOLS Melvin De Groote, University City, and Arthur F.

Wirtel and Owen H. Pettingill, Kirkwood, Mo., assignors to Petrolite; Corporation, Ltd., Wilmington, DeL, a corporation of Delaware Application November 1, 1949, Serial No. 124,816

7 Claims. (01. 260-611) :The present invention is concerned with cer'- tain new chemical products, compounds, or compositions which haveusef-ul application in various arts, It includes methods or procedures for man-- uiacturing said new chemical products, comor compositions, as well as the products, compounds or compositions themselves.

"We have discovered that if'one treats paracyclohexylcyclohexanol with acombination of propylene oxide and ethylene oxide within the proportions hereinafter specified, the mixed para-cyclohexylcyclohexanol glycol ether so ob-[ tained is an unusually effective demulsifying agent for water-in-oil emulsions and also has utility in various other arts hereinafter described. One specific example exemplifying the herein contemplated compounds is the product obtained by reacting one pound mole of para-cyclohexylcyclohexanol with 18 pound moles of propylene to yield the corresponding glycol or polyglycol derivative. Such oxyalkylated derivatives are readily prepared from chemical compounds in which the hydrogen atom is directly attached as oxygen, and particularly in the case of alcohols oxide, followed by reaction with 21 pound moles of ethylene oxide. Such oxyalkylations are usu ally conducted in presence of an alkaline catalyst and actually produce a cogenericmixture. This specific compound, or better still, cogeneric mix ture, just mentioned,'is' only one ofa series of similar compounds or mixtures having, in' the main, the same general structure or composition. Previous reference has been made to the fact" that the herein specified products are of particu lar value for resolving petroleum emulsions of the other purposes," such as a break-inducer in the doctor treatment of sour hydrocarbons; as an 5,

emulsifying agent, as a component in the prepa ration of 'mic'ellar solutions,- as an additive to non hydrocarbon lubricants, as an intermediate forfurther reaction by virtueoi the terminal hydroxyl-radical, etc."--- I J i It is well known that a variety of chemical" 7 compounds containing a reactive hydrogen atom,

i; e., a hydrogen atom attached to oxygen,nitrogen or sulphur, will react with alkylene oxides particularly ethylene oxide or propylene oxide,

or phenols, such as aliphatic alcohols, phenols,

alkylaryl alcohols, alicyclic alcohols, phenoxyalkanols, substituted phenoxyalkanols, etc. Gen

erally speaking, it has been-found advantageous to react a water-insoluble hydroxylated material, having 8 carbon atoms or more, with an alkylene oxide so as to introduce water solubility, or at least significant or distinct hydrophile character, with the result that the derivative so ob tained has surface-active properties,

Examples of suitable reactants of this type include octyl alcohol, decyl alcohol, dodecyl'alco hol, tetradecyl alcohol, octadecyl alcohol, butylphenol, propylphen'ol', propylcresol, hexylphenol,"

octylphenol, nonylphenol, and cardanol, as well as the corresponding" alicyc'lic alcohols obtained by the hydrogenation of the aforementioned phe-' nols. "It has been" suggested that at least some" of such materials be used in'the resolution'of petroleum emulsions. As far as we are aware; none 'of' suchmaterialsrepresent products whichare acceptable in demulsification today from a-' com petitive's'tandpointl Inth'e'majority of cases such products are apt to be one-sixth, one-fifth, one-fourth, or one-third as goods as available demulsifying agents on the same percentage-ob active-material basis, or'same cost basis.

We have discovered a very few exceptions to} the above general situation. For example, we; have discovered, if one treats para -cyclohexylcyclohexanol with ethylene oxide and propylene Q oxide so as to yield a cogeneric mixture of glycol ethers, that such mixed derivative has unusual properties, provided the composition lies within a certain range, as hereinafter specified. A specific exemplification of this range is'the product u obtained by treating one mole otpara-cyclohex f ylcyclohexanol with 18 moles ofpropylene oxide, 1

and then with '2 1'mol'e:s of ethylene oxide. Similarly, one ,may, treat the para cyclohexylcyclo hexanol with the 21 moles of ethylene oxide first andthen with the 18 moles of propylene oxide next". t

subsequent paragraphs fromtime to time; reference is made to ..compounds or cogeneric, mixtures. At first; glance, it may appear that such language is indefinite; and perhaps, contradictory.- It is the intention at the moment. only to point out that there is no inconsistency in such description; and that,"subseduently, there will be a complete explanation of why such designation is entirely proper.

Para-cyclohexylcyclohexanol is obtained by the hydrogenation of phenylphenol. The procedure is essentially the same as'is employed in the conversion ofphenolto cyclohexanol. The molecular weight is 182'.

' The cogeneric mixtures of glycol ethers of paracyclohexylcyclohexanol are unusually effective demulsifying agents on a comparatively small number of oil field emulsions, which, .oddly' mulsifying agents. However, such 1productshave significant utility in a number of different oil fields where they serve better than any other available demulsifying agent. Their utility may, of .course, increase as time goes along. I

It is very peculiar that the effectiveness of the demulsifying agents herein described seem :to be limited to a very narrow range or area as far as composition goes.

Reference is made to theaccompanying drawing in which there is presented a triangular graph showing the composition of certain glycol'ethers of para-cyclohexylcyclohexanol, or cogeneric mixtures thereof, derivable from para-cyclohexylcyclohexanol and ethylene oxide alone, or para-cyclohexylcyclohexanoljand propylene oxide alone, or para-cyclohexylcyclohexanol and both propylene oxide and ethylene oxide,initerms of the initial reactants. We have found that effective demulsifying agents lie approximately within a small and hitherto unsuspected area indicated by the trapezoid of said graph determined by the points -8, 9, l0 and II. More specifically, particularly effective demulsifying agents appear within a smaller range,-as set forth approximately by the areaindicated jbythe segment of acircle in said graph, in which the area of the seg- 4 can be made in three different ways: (a) by adding propylene oxide first and then ethylene oxide; (12) by adding ethylene oxide first and then propylene oxide; or (c) by adding the two oxides by random, indifferent, or uncontrolled addition so as to. produce a polyglycol ether which the propylene radicals and ethylene radicals do not appear in continuous succession but are hetero- "geneously distributed.

We have found that if propylene oxide is added first and .then' ethylene oxide is added, the compounds or cogeneric mixtures so obtained are invariably and inevitably more effective as demulsifiers, and are also more efiective for otherpur'poses thanthe comparable glycol ethers. of -para-cyclohexylcyclohexanol made by com bining, the three reactants in any other sequence.

This will be explained further with additional 11- c .lustrations subsequently.

ment is limited to derivatives in which paracyclohexylcyclohexanol contributes at least 4% by weight of the ultimate compound or coge the points I, 3 and 6 appear on the circle. The.

more effective of these better compounds or cogeneric mixtures are those which appear within the triangle which represents part of the circle and part of the segment, to wit, the triangle identified by the points I, 3 and 6. The most efiective compounds or cogeneric mixtures of all are those which fall within the inner central triangle of the larger outer triangle identified by the points I, 3 and 6, to wit, the smaller triangle identified by the points 2, 4 and 5. The most outstanding of these efiective compounds or cogeneric mixtures is one which appears to fall substantially at the center of the smaller triangle,

identified by pointl. This particular point is obtained by treating one mole of para-cyclohexylcyclohexanol with 18 moles oi propylene oxide, followed by treatment with 21 moles of ethylene oxide.

In spite'of the unique character of the cQmQ: pounds or cogeneric mixtures previously described we have made additionall'yan invention within an invention. This can be illustrated by reference to the compounds or 'cogeneric .r'nixtures whose composition is determined by the inner triangle. 7 I This preferred class of derivatives, or, for; that matter, all the herein described products,

As an illustration of tlie preparation of various compounds or cogeneri c mixtures, and particularly the vmost desirable ones, and also those;

w h a helpful i s t n t e l m t e; graph previously referredto, the followinge amples are included. In, connection with ment with ethylene oxide or propylene ox a i ure of V the twp. i ie nxeni ene t procedure is conducted in thesame manner em}, ployed in connection with other alcohols; pr {the} like, and generally an .alkalineacatalystis e ployed. V v

The reaction vessel employed was ;a stainless.

steel autoclave i heiu u devi ee er heat control, stirrer, inlet, outlet, etc.,which is conventional in this type of apparatus. q'lhe ,c

pacity was approximately 4 0 gallons. The stir ier operated at a speed of approximately 250 r. p..-m. There -were charged 7 into the autoclave 18.2; pounds of pare-cyc1ohexylcyclohexanol. f-Iihei ee e a d /2 unces fi p re a el zfivb. by weight) of ground caustic soda. The autoclave was sealed, swept withnitrogen gas, and stirring started immediately and; heat applied, and the; temperature allowed to rise -toapproximatelyl50.

C. At this point addition of-propylene oxide was started. It was added continuously at such-speed that it was absorbed by the reactionas rapidly;

as added. The amount of propylene oxide added was 104 pounds. The time required to add this propylene oxide was slightly in excess of one hour, about 1%, hours. During this time .the tempera ture was maintained at to .C., using cooling water through the inner coils when necessary and otherwise applying heat if required. At the end of the addition of the propylene oxide there was added ethylene oxide, as previously ndicated. The amountof ethylene oxide added was 92.4 pounds. The temperature employed, andop erating conditions, were the same as with the' addition of propylene oxide. It is to be-.noted,- however, that ethylene oxide'appears to be morereactive and the reaction seems to requires was held at approximatelyfio pounds per squarey inch gauge pressure, or;less. When -all:theoxide a been, added h 1ene xid b g th -1111. 5

additieninthispartieularinstanee) theautoclave;

was permitted to stay atthe same temperature rangeioranother half hour, even longer, it; re-

quired, or until the gaugepressure hadbeen re- The same procedure as in Example 1, preceding, was conducted on a laboratory scale employ- 6: in the laboratory autoclave, in, a fraction of: the time.- requi n e lar er autoclave; in fact. many instances absorption was complete-in 5 to or minutes, as compared to, one hour on a ducedgtozeroor substantially zero, indicating the 5 large scale. Needless to say; on, a largescale reaction waseomplete. Thefinal product was an addition must be conducted; carefully, because material, somewhat viscous in. nature, re-J there is an obvious hazard in handling a large Pastor Oil i ha ng an Odor- $q V quantity of material in an autoclavewhich is not, t para-cyclone):ylcyclohexanol. It was soluble necessarily present in the use of a small vessel. inwater and also solublein non-aqueous solvents, 10 Exam le 5 I such as aromatic hydrocarbons, and others, alp r e though not soluble in somenon-polar hydrocar- The. same procedure was followed as in Ex-j borr solvents. The final yield was substantially amp pr cedin n every pect, except. h total. weight of the. initial reactants. zlariatilgnldescribeg in, Example 2, preceding, i. e., e e y ene oxi e, was, added first, andv the Example 2 propyleneoxide added last. 'The'sameprocedure was followed as in, Example Example Lpreceding, except that the order of, addition of tlijeoxide's was reversed the ethylene oxide being T e same. procedure was followed as added first and the propylene oxide last. The 20, 3 13 8 in every insta c ex p h m d fl ar time period, temperature range, pressure, etc, tion previously described in Example 3, to; wit, werekept the same as in Example 1. preceding. 19h}? P py de and the ethylene oxidewer Exam Z 3 7 mixed together and added in approximately 15 p 6 minutes to one-half hour. In all other respects] 'f'ilie same procedure was followed as in Example the procedure was identical with that described Lexcept that a mixture, to wit, 196.4 pounds of in Example 4. propylene oxide and ethylene oxide, were added The following table includes av series of 001:1'1'1 overa two-hour period. This mixture of ethylene pounds or cogeneric mixtures which have be n oxide and propylene oxide was obtained from 104 selected as exemplifying the herein included pounds of propylene oxide and 92.4 pounds of products. Types of the herein noted compounds ethylene oxide. In this instance again the time or cogeneric mixtures have beenproducedinthreel range, temperature, and pressure were kept the difierent y (a) first adding propylene oxidef same as in Example 1, preceding. and then ethylene oxide; (b) first adding eth-.-. Example 4 ylene oxide and then propylene oxide, and (c) mixing the ethylene oxide and the propylene oxide together and adding them simultaneously.v The data are summarized in the following ing a small autoclave having a capacity of table:

Para-Cyclohexyl-Cyclohexanol Propylene Oxide Ethylene Oxide Paint an rap ' Identi- EX. No. Wt. Wt. Per Wt. Wt. Per Wt. Wt. Per lying Used, Molal Cent in Used, Molal Cent in Used, Molal Cent in S has.

in Ratio Final, Glyin Reno Final Glyin Ratio Final Gly- G ycol Grams 7 col Ether Grams col Ether Grams 'col Ether- Ether 182 1. [l 15. 0 546 9. 42 45. 0 486 11. 05 40. 0 1 182 1. 0 10. 0 912 15. 72 50. 0 730 16. 6 46. 0 2' 182 1. D .5. 0 2, 008 34. 6 55. 0 1, 460 33. 2 40. 0 3 182 1. 0 10. 0 820 14. 12 45. 0 820 18. 7 45. 0 4 182 1. 0 5. 0 1, 825 31. 5 50. 0 1, 645 37. 4 45. 0, 5 182 1.0 5.0 l, 640 28. 3 45. 0 1, 825 41. 5 50.0 6 182 1. 0 8. 5 1, 040 1,7. 95 48. 5 924 21. 0 43. 0. 7"- 182 1. 0 9. 8 912 15. 72 49. 0 766 17. 4 41.2 182 1. 0 9. 5 930 '16. 05 48. 5 806 18. 35 42. 0 182 1. 0 9.2 938 16. 15. 47. 4 860 19. 55. 43. 4 182 1. 0 8.8 955 16. 5 46. 2 932 21.15 45. 0 (l) 182 1. 0 8. 5' 1, 040 17. 95 48. 5 924 21. 0 43. Q 182 1. 0 8. 5 1,040 1.7. 95 48. 5 924 21. 0 43. 0 182 1. 0 '8. 4 1, 012 17. 46. 6 .976 22. 1 45. 0 182 1.0 8.2 1, 100 18. 95 49. 5 940 21. 35 42. 3 182 v l. 0 7. 8 1,112 19. 2 47. 6 1, 04,0 23. 44. 6 4' 182 1. 0 7. 5 1, 168 20. 1 48. 2 1,075 24. 45 44. 3 182 1. 0 7. 0 274 21. 95 49. 0 1,145 26. 0 44. 0 132 1. 0 6. 0 1, 500 25. 9 49. 4 1,352 30. 75 44. 6 182 1. 0 20. 0 236. 5 4. 07 26. 0 491. 5 11. 15 54. 0 182 1. 0 4. 0 1, 182 20. 4 26. 0 3, 182 72. 4 70. 0 2 182 l. 0 4. 0 3, 460, 59. 6 76. 0 910 20. 65 20. 0 182 1. 6 20. 0 546 9. 41 6D. 0 182 4. 14 20. 0 2

1 Within inner triangular area. 1 Duplicated for convenience. 3 Indicates limits of trapezoidal ares.

approximately one liter, or up to a 5-gallon size. as 'In the preparation of the above compounds The amount of terpineol employed was 36.4 grams, the amount of propylene oxide employed was 208.0 grams, and the amount of ethylene oxide-employed was 184.8 grams. The amount of caustic soda used as a catalyst was 2.33 grams. The operating conditions were substantially the same as. on a larger scale. seemed to go faster in the small autoclave and the 1 time of absorption could be reduced, if desired. Ii -"many instances, absorption would take place 75 one obtainsa cogeneric mixture of closely related Actually, the reaction 1 the alkaline catalyst used was either flake caustic soda finely ground with mortar and pestle, orpowdered sodium methylate, equivalentto 5% by weight of the para-cyclohexylcyclohexanol which was employed.

For reasons which are pointed out hereinafter i in greater detail, it is substantially impossible to use conventional methods and obtain a singleglycol ether of the kind described.v Actually.

7: or touching 'homologues. "These materials "in? variably have high molecular weights and cannotbe separatedfrom oneanoth'er by any known method without decomposition. The properties of such a mixture represent the contribution of the various individual members of the mixture. :.Although one cannot draw a single formula and say that by following such andsuch pro cedure one can obtain 80% "or 90%oi' 100% of such single compound, yet one can readily draw AMA If one selects any hydroxylated'compound and subjects such compound to oxyalkylation, such as oxyethylation or oxypropylation, it becomes obvious that one isreally producing a polymer of the alkylene oxide, except for the terminal group. This is particularly true where the amount of oxide added is comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such a compound'is subjected to oxyethylation so -as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent, which, for sake of convenience, may be indicated as RO(C2H4O)30H. Instead, one obtains a cogeneric mixture of 'closely related homologues in which the formula may be shown as the following: RO(C204)11.H, wherein n, as far as thestatistical average goes, is -30,-but the individual members present in significant amount may varyfrom instances w here n has a'value of This means that from the practical standpoint description.

matne'mauesrexaminauon.yer indicating the ex; 7

act proportion of the various members of 'touch ing homologous series which appear in cogeneric condensation products of the kinddescribedQZ i. e., the ability to describe how 'to' make product undercd'risiderationand how to repeat such production time aftertime without difl lculty, it is necessary to resort to some other method of Actually, from,a,.practical standpoint it ismuch more satisfactory; perhaps, to describe the nitimatecompos'itio'n in terms of the reactantai; e5; paracyclohexylcyclohex'anol and the 'two 'alkylene; oxides. The reason for this statement is'the'folf-I; lowingzlf one-semen a specificcompound it must, be borne in mind that such compound is specific only insofar that the .cogeneric mixture in terms of a statistical average will conform to this formula This maybe illustrated by an example; such as RO(C3H6O 1s'(C zH O) 21H. "If one come"v bines the reactants inthe predetermined weight ratio so as-togive theoretically this specific come, ponent, .and. assuming that only one chemical compound were formed, .What happens is.that,falthough this particular compound may be pres-,1

ent in a significantamount, .and probably less};

than actually, one obtains a cogeneric mixture of touching homologues iniwhich the statistical average -does :ccrrespond to this formula.

R0 (CsHeO). 1s,(C2H4O) 21H what actuallyhappens-is that one obtains a sort 'of double 'cogeneric mixture, for the reason that gin each-batch or continuous addition of an alkyll-ene oxide a cogenericmixture is formed. Since the present products require the addition of at least two different .multi-moiar-proportions of h each of two different alkyleneoxides-(ethylene oxide and propylene oxide) j "it becomes obvious that, a rather result. I

complex cogeneric mixture must This can be best illustrated-by example. As-

ffsume that one,v is goingto use the indicated ratio,

.. n hi nili r f ar .ldresen i amounts of hdmologues in which n varies from 10, 11 and 12 on up to 23, .24 iand possibly 25-01 26. A statistical average; however, must, of course;

correspond -to'the;proportion of the initialre actants, -i. e., a compound of the formula; RO(C3H5O) ;;H .which is present undoubtedly to; asignificant extent.

AWhen this;;cogeneric;mixtureis thensubjecteda to reaction with 21-moles of ethylene oxide, ,xitarbecomes obvious that, although one may obtain some RO(C3H6O).18(C2H4O) 21H, .yet this .particu-i' r! lar. product can beepiesent only toaminor extent; a.

for reasons whichmave :been described in-con nection with oxyethylation and which-now ia'rel magnified to a greater degree by oxy-propylation. scared another way,it probable that the cogelleric mixture represents something like in. moii amounts, the percentage of such componentsdecreasing, the further removed they are from the average composition. However,- in spite.

of such variation in regard to the 'cogeneric mixh re, the ultimate composition, based on the in- V gf'dient's which enter into it and based on the statistical average er suchconstituents, can still expressed by the formula RO(C3'H50') 18(C2H4'0) 21H This actual product exists, to some degree, in the eegenerl mixture, but it should be looked upon as'j'astatis'tical average formula, rather than the structure of a single or predominant compound ll tne mixture. 1

"eeorld reason for employing a reaction mixtfilf to" describe" the product, is the fact that the mdlalproportions need not represent whole numblis. W6 have jlls't pointed out that if one selects molal proportions eerrespondirlg to RO(C: "H60) 18(C2'H4O) 21H t n. theconstituents are added in actual molar r p portions, based on whole numbers. If, howe r, onesel'ects a point in the inner triangular er the accompanying graph, which, when recalculated in terms of molar proportions, produces affactional number, there is still no reason why proportion of initial reactant should riot 'beadopt'ed. V For instance, one might select a point ii'i t'lie triangular graph, which, when calculated terms of molecular proportions, represiitsa formula, such as the following:'

RQ( CsHeO l'lat ((321-140) 21H ihis, o1 course, would be immaterial, for the reason that if one startswl-th a pound mole of para-cyclohexylcyclohexanol and adds 18.5 pound Such mixture could, of course, be treated 21 pound moles of ethylene oxide. Actually, all that has been said sums up to this, and that is, that the most satisfactory way, as has been said before, of indicating actual materials obtained by the usual and conventional oxyalkylation process is in terms of the initial reactants and it is obvious that any particular point on the triangular graph, from a practical aspect, invariably and inevitably represents the statistical average of several or possibly a dozen or more el'eeely related-cclgeliers of almost the same camposition, but representing a series of touching" homologues. The particular point selected represents at least the composition of the mixture e'xpressed empirically in theteliiis o'la compound representing the Statistical average.

Previous reference has been made to. the fact that comparatively lew oxyalkylat'eol derivatives of simple nyero'xylated corll ounas' ii'nd utilit in actual demlzlslrlc'ation practice. We have olnt= ea outthat we havefound a very few exceptions to this rule; The fact that exceptions exist, as me instant invention, is stlll'exceedln'gly dll= ficult to explain, if one exar'nines the Slight contribrition that the end group, derived IlOm the" hydroxylated material, makes to the entire com pound: Relerring, for the incilne'n't, to" a prod uct of the kind which has been described and identified by theformula 1 2o it be'comes apparent that the molecular weight is iri'theneignborhood of 2100, and actually, the; para; cyclonexylcyclohexanol contributes less than 1 0% or the molecular weight; As a matter of fact, in other com-parable compounds the paracycloliexylcyclohexanolmay contribute as little as 4% or 5% and yet these particular compounds festive. Actually, this not the case. Wexnow' of no theory or explanation to suggest thishighly specific nature or action of the c'ompoundor cogeneric mixture derived cyclol'lexan'01.

Referring: to an examination or the previouslist or 32- compounds, it'is te be notedthat ln 'eer t'a'i'n examples, for instance, Examples 9 to 15, in clusi'v'e', all the propylene oxide is added first and:

, the ethylene; oxide is added; compounds indicated by Examples 1 t0 8 afe'sub stztflfilally the same as 'far' as composition goes, but are reversed, iii'so I far that the ethylene oxide is added firstahel thii the prop lene oxide: Other compoundshaving" substantially the same ultimate coin-position, or

at Iast V61"? GIOS'ely' related ultimate compositions, Having 8) runner variatio in the distribfitidii 6f the prop lene ex d'e and ethylene ox id, are xliipllfid by Ferrell-lee 1 6130- 3 2',- incli'i reason which we do' not-understand and for which we have not b'eeriable to (alter any satisfactor'j thBOIY WG have found that the best compounds, or, more properly, cogeneric mixtures; are obtallied whenall th'e'propyleiie oxide is added first, then al11' the" ethylene oxide TS added". All 1 though this is true at leQStsbnieQxtflt in 1'65 gard to all compos tions" within the trapezoidal area the triangular graph, yet it is partic'u- 'larl'y truej iithe composition comes within the segment' of theicircle' of the accompanying drawing'; in suchevent, one obtains a much moreeffestive, demulsifier than by any other combinatijon? employing ethylene oxide alone", pro ylene oxidealone, or aiiy'variation inthe mixture of the twdfl'a's illustrated by other formulae. met; the 'co'mpound or cogeneric mixturesoobtamem s far as demulsificationis concerned, le not infrequently at least onethird better than;

any'other derivative obtained in the manner defroln para-.cyclonexyn- As has been perm-eel out previou ly; for" seine scribed involving .any the other above v a ria;

tions.

' The. significance. ofwhat'has been said previouslybecomes more emphaticwhen one realizes that, in essence, we. have found that one isomer isa more effective.demulsifyingfagent than an other isomer'. The word isomer? isnot exactly right, although it descriptive" for, the purpose intended insofar thatwe afe' not concerned with asingle compound, but with: a cogeneric mixtu'r'e, which; it" is statistical average, corresponds to such compound. "Stated another way, if we start with one poundimol'eof para-cyclohexylcyclohexanol, 18 pound molesofpropylen'e oxide and 21 pdund moles or ethylene oxide, we can prepare two. difirentfcogenericimixtures, which, on a statistical average, orr'es'pond to the followings RO (C2H40)21(-C3HaO)'1aH- and RO (C3HsO) 18(C2H40) 21H There is nothing we know which would suggest that-the latter be. a. muchsmoreeffective.demulsi tying agent than the. formerrandealso. that. it .be. more efiectivefor otherindustrial. purposes. The. applicantshavehad wideexperience witha wide. variety. of. surfaceractive. agents, but, they. are. unaware of. any. other, similansituation, withthe. exception .of a. few .-instances. which are the, sub..- jectematter of other,co:pending..applications, or. undeninvestigation... This feature. represents the. invention within .an invention .previouslyreferred. to, and .thus, becomes-.thelspecific.subjectematter claimed. in, ouricoy-pending, applications. Serial Nos. 124,817, now. Patent. No. 2,558,513,. .and. 1251 818, both filedNovember .1, 19.49.. .r

Reterence.hasbeenmade tov the. fact'thatthe product hereinspecified andparticularly. for. use; as a demulsifier, represents a cogenericmixture. or; closely re ated homolo uesr This, does not mean, that. .Qne .coulddnp tiruser. combinations of such co e eric, mixtures... Forinst c in the nrev oustable, data. have been given. ,fQr pI$pa1a,-, t onof,coeener qmixtur s wh ch. statistically. cor: espond, res ctivelyr.tmpo nts. I., tend. 6.. Such. ree, oo sner s mixtu es. could.. be combinedin qual. weishtssoasl q eiveacqmbinat onin. which he. m xed. sta istiq layera e.would;..sorremond.

lo e r tepointf fiim lar mj o eco dfld hesame. thin y .pre.-. palms. c ne ic...mist :es.. corre pondin to. poiu tends; essrib din the previ us table.- uqh x re c uld. then... be; combined-me equal; parts by weight to give another combination hich w u d c ose y. c rre pond. .9 .am xsd staist a asis; o, PQ nt thin is icherenr s. n en d er wmqs. s mmhiaa pns Oit s. orflsirnilar type.

' We, need, not add that instead; of. subjecting A para-cyclohexylcyclohexanol alone to ,oi;yethyl a tion and oxypropylation, orf inversely to 03y; propylation and oiryethylation, of simultaneous treatment with both oxides,- one can employ a mixture of cyclohxylcyclohxanol along, with some other desired reactant sucu- 'asfalphater". pineol. For a number of reasons", itv ordinarily desirable to use a Qp'rocedurefin which'only' on product is reacted ata time.

T hout t e s ecifica i e ewh r e er: ence has been made to homologues. Itjis quite likely that it would .be equally proper, in nume ous instances, andperhaps' in all "the herein "dee scribed products, to refer to isomers, aswell' as homologues. The reason for this statement is that propylene'oxide asdiflerentiated from ethmer has been used thus: isomer? It not believed there is any conf;usionb 'etween such ter minology in that particular instance and'what is mm die l pr c di s,

' Attentionis direetedto the factthat the hel i'r in 7 described compounds, compositions and the I like which are particularly adapted for use ows;

demulsifiers for water-in-oiljemulsions, as found in the petroleum industry, are hydroxylated derivatives, .i. e., carry, or include a. terminal hydroxyl radical as part of their structure. have found that if such hydroxylated compound. or compounds are reaetedfurther so as to pro-.1 duce entirely new derivatives, such, new, deriva'. tives have the properties of the original mare -g ylated compound insofar, that they are effective I andvaluable. demulsii ying; agentsffor resolution of water in-oil emu sions'as .found 'in 'the 'pe '.-.f. troleum industry, as break inducers.- in doctor? treatment of sour'crude, etc.

Such hydroxylated compounds can be treated with various ,reactants. such ,asglycide, epichlorohydrin, dimethyl sulfate, sulfuric acid, maleic, anhydride, ethylene imine, etc. Iiftreated epichlorohydrin or monochloroacetic acid, there;

sultant product'can be furtherreacted with a tiary amine, such s'pyr dine; rthe ike; o ve 7 reated? qu t n m on m omroundswi hg le a h ride to s v ;.a" ot 1 ster; h. resultan a be. eatedw hs m 'sulfit i yielda chlorosuccinate, Sulfo groups can be inddu ed l oby. mean tjra-sul at n ag nt. s

previously e seste or. y tre t ng. ejchldroi acetic acid-resultant with sodium su1fite.' However, the-classof; derivatives. most readily prepared in wide variety are the esters of mono:

carboxy and polycarboxy acids.

Assuming a typical derivative which can be indicated-thus;

' RO (C3H5O).n (021140) Mn the ester of the monocarboxy acid is asiollows;

The. acid ester. of a dicarboxy acid is as iollows z The; chloroacetic acid ester. ,is, as ,follows r The quaternary compound obtained by reacting the abovementioned product with pyridine is as follows:

-nmcimonwrrumi-gcan Q the various kinds of monocarbo'xy acids suitable-for preparation of esters are the alphafialogen' monocarboxylic acids having 'not over 6 prayed to furnish the aeyl radical of the ester.

this particular instance, as in all other instan e one may prepare either a total ester or a partial ester, and when carboxy aci'ds are employed, one may have not only partial esters which have residual hydroxyl radicals or residual carlie-iryl -radicals, but also partial esters in which both are present.

A- somewhat similartype ofester is obtained .rrcm hydroxyacetylated drastically-oxidized castor ciL fatty acids. It is to be pointed out that liydroxyacetylation may take place first, anddr astic oxidation subsequently, or the reverse-may be true,"or both procedures may be conductedsimultaneously. In any event, such products supply acyl radicals of one type of ester herein included.

Another somewhat similar class are esters-obtained from hydroxyacetylated drastically-oxidizeddehydrated ricinoleic acid. In this classricinoleic. acid, castor oil, or the like, is subje'cted .to. dehydration as. an initial step. Such products, may be employed to supp y the acyl radicalof-onetype of ester herein included.

1: Another type of ester which may be employed is a sulfo fatty acid ester in which there-is presout atleast ii and notmore. than 22: carbon atoms in the fatty acid radical. The suite radical in-. chides both the. acid sulfonates and. the sulfonic employed .as' reactants are sulfo-ol'eic, sulforicinoleic, sulfo-aromatic fatty acids obtained,

fer example, from benzene, toluene. xylene, etc.,

androleicacid, or some other. unsaturated acid.

znnother class of acids are polycarboxy acids tartaric acid, citraconi'c acid, phthalic acid, adipic acid, succinic acid, azeleie acid, sehacic acid,:ad'-.

dilctacids obtained by reaction between. maleic anhydride, citraconic anhydride, and butadie'ne, diglycollic acid, or cyclopentadiene. Oxalic acid is not quite assatisfactory as some of theother.

acids, due to its tendency todecompose. i In light at ravlr material costs, itiis. our preference? to use phthalic anhydride; maleic anhydride, citraconic.

dnhydride, diglycollic acid, adipic acid and certain: other acids in the same price range whichareboth cheap and heat-resistant. One may also:

adduct acids of the them or Clocker type.

Briefly stated, suitable sulfo acids: herein 14' certain high molal monocarboxy acids. It is well known that certain monocarboxy organic acids containing 8 carbon atoms or more, and not more than 32 carbon atoms, are characterized by the fact that they combine with alkalies to produce soap or soap-like materials. These detergent-forming acids include fatty acids, resin acids, petroleum acids, etc. For the sake of convenience, these acids will be indicated bythe formula R.COOH. Certain derivatives of de'-- tergent-forming acids react with alkali to produce soap or soap-like materials and are the obvious equivalent of the unchanged or unmodified detergent-forming acids. For instance, in-' stead of fatty acids, one might employ the chlorinated fatty acids. Instead of the resin acids, one might employ the hydrogenated resin acids;- Instead of naphthenic acids, one might employ brominated naphthenic acids, etc.

The fatty acids are of the type commonly referred to as higher fatty acids; and, of course, that is also true in regard to derivatives of the kind indicated, insofar that such derivatives are obtained from higher fatty acids. The petroleum acids include not only naturally-occurring naphthenic acids, but also acids obtained by the oxidation of wax, parafiin, etc. Such acids may have as many as 32 carbon atoms. For instance, see U. Patent No. 2,242,837, dated May 20, 194 1, to Shields.

The monocarboxy detergent-forming esters of the oxyalkylated derivatives herein described,- are preferably derived from unsaturated fatty acidshaving 18 carbon atoms. Such unsaturated fatty acids include oleic' acid, ricinoleic acid,

linoleic acid, etc. One may employ mixed fattyacids, as, for example, the fatty acids obtained from hydrolysis of cottonseed o'il', soyabean oil, etc- It is our ultimate preference that me esters of the kind herein contemplated be derived from unsaturated fatty acids, and more especially, unsaturated fatty acids containing a hydroxyl radical, or unsaturated fatty acids Whichhave been subjected to oxidation. In addition to synthetic carboxy acids obtained by the oxidation of parafilns or the like, there is the somewhat analogous class obtained by treating carbon. dioxide or carbon monoxide, in the pres-- ence of hydrogen or an olefine, with steam, or

.' by causing a halogenated hydrocarbon to react with potassium cyanide and saponii'ying the product obtained. Such products or mixtures thereof, havingat least 3 and not more than 32 carbon atoms, and having at least one carboxylgroup or the equivalent thereof, are suitable as detergent forming monocarboxy acids; and another analogus class equally suitable is the mix ture of carboxylic acids obtained by the alkali treatment of alcohols of high molecular weight formed in the catalytic hydrogenation of carbonmonoxide.

One may have esters derived not only from a single class of acids of. the. kind described, but alsofrom more than one class, i. a, one may-- I employ mixed esters such as esters obtained, for

example, from high molal detergent-forming, acids. having 8 to 22 carbon atoms, as previously described, in combination with acids of the alpha. halogen carboxy type having lessthan 8 carbon atoms, such as chloroacetic acid, bromoacetic acid, etc., asprevi'ously described.

Drastically oxidi'zed oil, such as drasticallyoxidized castor oil, or drastically-oxidized dehydrated castor oil, may be employed to supply Qinother. class. of esters-arederived from 5,; the acyl'radicah -In-"othe1-instances, one may Ii-i pr ueemixed stersbxusin polycarboxracids. such; as -phthalicacid, diglycollic, acid, etc., in ombin on. wi .detereen fiormin acids, Such as oleic acid, stearic acid,,naphthenic..acid, etc.

Other ,carboxy acids may be employed in which there is also a. su l f o .group present, such .as..sulf.o: phthalic, sulfo benzoic, su1f o succinic,; etc. Ewters may be, obtained from low. .molal hye. droxylated acidshaying less than 8 carbonatoms, such as hydroxyacetic. acid, lactic. acid; etc. Sin ilarly, one may employ, low molal aliphatic acidshaving less than 8 carbonv atoms, such, as aeetie acid, butyricacid etc. Similarly,.one.may empleylow molal acids.,ha ving the .vinyl radical, such, as acrylic, acid, rnethacrylic acid. crotonic acid, etc. It willbe notedthat.theselacidscons tain various numbers of acyl radicalsvarying generally .up to ,22. carbon atoms. for. the .monoe carboxy acids, and asgmany as.36 .carbon atoms inthe case of certain polycarboxy acidsparticularly the dimer obtained, by the dimerization .of 9,;1l-octadecadienic acid. Asxto, this particular. product, see IL 8.. Patent .No. 2,347,562, dated April25, 1944, to Johnston.

Other. suitable acids are cyclic .monocarboxy. acids having notover. 32 carbon. atoms. Ex.- amples of such acids, include, cyclohexane acetic acid,cyelohexane butyric acid, cyclohexane.pro-. pionic acidycyclohexane caproic. acid, benzoic acid, salicyclic acid, phenoxyacetic acid, etc.

The preparation of such esters are...conventional and do not require elaborate description. Generally speaking, our procedure is .to react the. approximate amquntof ,a selected hydroxylated compound with the free acidin presence of, a high boiling solvent, such as xylene, using 1% or 2% of para-toluene sulfonic acid, alongv with. .a. phase-separating, trap until the amount of water.- indicates the reaction is complete, or.substan-.-. tially comple te. The time required is, usually .4 to 20 hours. Such esters are, as previously stated,- very efiectiveior resolution of water-in- -oilemule s'ions, as found in the petroleum industry.

The triangular graph. represents the, threecomponent system, Using 4 reactants, i. e., the. three depicted in the triangular graph, plus .glycr. ide gives a four-reactant system ,whichyields derivatives atleast equal for demulsification. of water-in -oil emulsions to those herein described. Theuse of glycideina f our-component reactant permits unusual structure, as, for example, ,a variety of furcation, Thus, the hydroxylated initial reactant canv he treated with glycidein the conventional manner, using an alkalinecatalyst, and'after an. introduction of a. mole-011 mole ratio of glycide, then propylene oxide can. be introduced in the manner previously described, andthereafter ethylene oxide can be added. Ifv desired, the propylene oxide can be introduced.

first and then one mole of glycide added, followed 1 by ethylene oxide, or both procedurescan be employed.

. Moreover, glycide can be used to replace a substantial part or greater part of-the ethylene- 65 oxide, or propylene oxide, or both. Such com-- pounds can be converted into various derivatives ofthe kind previously described. Under such' circumstances, reaction with glycide' and an end reactant to supply aterminal-radicalfis not con-I sidered as forming a derivative, but as simply.

forming the end material. The ester and similar' derivatives so obtained from the fang-component iginal y t .e' e n nc di ycide... a s veryefies ye. 9 r unific tion oi..-

a d. w en ric me e in r vedex us retain- .1 mulsio s... as. qun v rrtbeoil in: tm

Having thus described our invention, whatgre. claim as new and desire to secure by Letters Patent is:

1. A new chemical product, comprisingat least one cogeneric mixture of a homologous series of glycol ethers. oi para cyclohexylcyclohexangl;' said cogene'ric'v mixture being. derived "excl ely from para cyclohxylcyclohexanol, ethylen d bibbvlefleloxideiin mhj f hti ier so the a em composm n' r said cogenerie ture" stated of, initial reactants approximatly'within 'theitrapefzoidal area o p thejl mannin drawiasf eflm approximately by points 8, 9, IQ and -l 1 I T ie s f i ui ahc ls usse ies 1 Q h E$ f.i 341?" Y 9h 9 9 mm ram1 yc qhex ty he a o .ethy en .d

d, Pr n e. Su h e h rqn r i s. ci-t e are esec m q ition sei .c s er ..mix,-; ture statedin terms, of initial reactants es ap roxim elr nin e ilez dal area-.01 rap e. t m n h draw nadefine n im e yr ints 8.1 ma d. 1-1.

cosen ric i ur ahqmqloequsse s. of yc l eth rs f .p ra-c l hex lc clohexan said cogeneric mixture being deriyedgexclusiy o P mrc c h xy clo exanol. ethy ne e and pr py n o de i h wei ht proportions so the average composition ,of said cogeneric mix; ture stated interms, or. initial; reactants. lies; approximately within. the Segmentbf. the -circle. of the graph in the.,,accompanying drawing im which the minimum .para cyclohexylcyclohexanoli content is at least 4% ,and which circlejsidentie.v fied by the fact that points I, 3 and 6 lie .on; its; circumference.

4. A cogeneric mixtureof a. homologous series. of glycol ethers. of para-cyclohexylcy,clohexanol;v said cogeneric mixture .being, derived exclusively... from para-cyclohexylcyclohexanol, ethylene oxide, and. propylene oxide in. such weight proportions so the averagecomposition of said cogeneric mix, ture stated termsof. initial reactantslies approximately within the. triangular. area'...of .the graph in. the accompanyingdrawing defined by. pointsl,3and6. M

5...A cogenericmixture. of a homologous series; of .glycol ethers. of para-cyclohexylcyclohexanol:- said. cogeneric mixture being derived exclusivelyfrom para-cyclohexylcyclohexanol,ethylene oxide and.v propylene oxide in. such weight proportion-s so the average composition of said .cogenericlmixe. ture stated in,. terms of initial reactants-lies approximately within the triangular Iarea of the graph in the accompanying drawingdefined -by points 2, 4 and.5. r

6. A cogenericmixture of ahomologousseries. of glycol ethers .of para-cyclohexylcyclohexanol;-- said cogeneric ..mixture being -derived'..exc1u'sively.i from para-cyclohexy1cyclohexanol,ethylene oxide; and propylene oxide in. such weight proportions so the average composition of said cogenericmix'fture stated in terms of initial reactants 1ies approximatelyatpoint 1 in the graph in the}. accompanyingdrawing. I r

7. A single cogeneric mixture of a homologous. series. of glycol ethers of para-cyclohexylyclo hexanol; said. cogeneric mixturebeing derived: exclusively i'rempara cyclohexylcyclohexanol,= ethylene oxide and propylene oxide in such weight. proportions so ,the average, compositionuofhsaldl eosemtiamixtme stated-in. termsiof-initiarreact-i ants lies approximately at point 1 in the graph REFERENCES CITED The following references are of record in the file of this patent:

18 UNITED STATES PATENTS in the accompanying drawing. Number Name Date MELVIN DE GROOTE- 2,130,525 Coleman et a1 Sept. 20, 1938 ARTHUR WIRTEL- 2,213,477 Steindorff et a1 Sept. 3, 1940 OWEN PETTINGILL- 2,425,744 Roberts et a1 Aug. 19, 1947 2,425,845 Toussaint et a1. Aug. 19, 1947 

1. A NEW CHEMICAL PRODUCT, COMPRISING AT LEAST ONE COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF PARA-CYCLOHEXYLCYCLOHEXANOL; SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM PARA-CYCLOHEXYLCYLOHEXANOL, ETHYLENE OXIDE AND PROPYLENE OXIDE IN SUCH WEIGHT PROPORTIONS SO THE AVERAGE COMPOSITION OF SAID COGENEIC MIXTURE STATED IN TERMS OF INITIAL REACTANTS LIES APPROXIMATELY WITHIN THE TRAPEZOIDAL AREA OF THE GRAPH IN THE ACCOMPANYING DEFINED APPROXIMATELY BY POINTS 8, 9, 10 AND
 11. 